EP0275579A1 - Storage-stabilized compositions based on vinylidene fluoride polymers containing a metal molybdate - Google Patents
Storage-stabilized compositions based on vinylidene fluoride polymers containing a metal molybdate Download PDFInfo
- Publication number
- EP0275579A1 EP0275579A1 EP87202405A EP87202405A EP0275579A1 EP 0275579 A1 EP0275579 A1 EP 0275579A1 EP 87202405 A EP87202405 A EP 87202405A EP 87202405 A EP87202405 A EP 87202405A EP 0275579 A1 EP0275579 A1 EP 0275579A1
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- Prior art keywords
- vinylidene fluoride
- stabilized compositions
- compositions according
- molybdate
- parts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
Definitions
- the present invention relates to storage stabilized compositions based on vinylidene fluoride polymers comprising a metal molybdate.
- Vinylidene fluoride polymers are hardly flammable and self-extinguishing. It has already been proposed to incorporate flame retardant additives therein in order to further improve their resistance to ignition. However, flame retardants have generally been shown to be incapable of completely preventing, at high temperatures, the combustion of articles made of vinylidene fluoride polymers. Furthermore, we now know that, contrary to the generally held opinion, the combustion of shaped objects made of vinylidene fluoride polymers causes the emission of smoke in sufficient quantity to constitute as serious a disadvantage as the flames themselves, insofar as it makes rescue operations more difficult.
- compositions based on vinylidene fluoride polymers which comprise metal molybdates have the drawback of turning blue when stored in a humid atmosphere. Although this bluing does not affect the fumicating efficacy of metal molybdates, the appearance of a bluish coloration seriously reduces the possibilities of using the compositions in question, in particular in the field of shaping of colorless or colored objects in shades clear, such as cable sheaths.
- the present invention aims to overcome the aforementioned drawback. To this end, it provides compositions based on vinylidene fluoride polymers comprising a metal molybdate whose color is stable on storage in a humid atmosphere.
- these compositions contain, as stabilizer, an effective amount of alkali or alkaline earth metal carbonate.
- All the carbonates of alkali or alkaline-earth metals and their mixtures are suitable for producing the compositions according to the invention.
- a very particularly preferred alkaline earth metal carboate is calcium carbonate.
- the amount of carbonate present in the compositions according to the invention can vary to a fairly large extent. Usually, carbonate is used at a rate of at least 1 part by weight and at most 100 parts by weight per 100 parts of molybdate. Preferably, it is used in an amount of 5 to 30 parts by weight in total per 100 parts of metal molybdate.
- metal molybdates and their mixtures can be used in the compositions according to the invention.
- Particularly preferred metal molybdates are calcium, zinc and aluminum molybdates.
- molybdate present in the compositions according to the invention can vary to a large extent, in particular depending on the result sought and the nature of the molybdate used.
- molybdate is used in an amount of 0.05 to 2 parts by weight, expressed as metallic molybdenum, per 100 parts of vinylidene fluoride polymer and, preferably, from 0.10 to 0.50 part.
- compositions according to the invention therefore contain from 5 to 30 parts by weight of alkaline earth metal carbonate per 100 parts of metal molybdate and from 0.10 to 0.50 parts by weight of metal molybdate, expressed as molybdenum metallic, per 100 parts of vinylidene fluoride polymer.
- vinylidene fluoride polymers is intended to denote all the polymers containing at least 85 mol%, and preferably at least 90 mol% of monomer units derived from vinylidene fluoride.
- the vinylidene fluoride polymers which are suitable for producing the compositions according to the invention therefore include both homopolymers of vinylidene fluoride and its copolymers containing monomeric units derived from one or more comonomers.
- polymers of vinylidene fluoride containing at least 90 mol% of monomeric units derived from vinylidene fluoride, the optional complement preferably consisting of monomeric units derived from other fluorinated olefins, such as vinyl fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene and hexafluorpropylene.
- compositions according to the invention can contain all the usual additives for polymers of vinylidene fluoride, such as lubricants, flame retardants, polymeric additives, etc.
- the compositions according to the invention contain at least 65% by weight of one or more polymers of vinylidene fluoride and, more often than not, at least 80% by weight of such polymers.
- the carbonate and the molybdate can be used in any form, in powder or in aqueous dispersion for example. However, for reasons of convenience, it is preferred to use them in the form of a powder. In this case, it is advantageous to use powders having a dimension of average particles less than about 200 ⁇ m. Preferably, this is less than 100 ⁇ m and more particularly than 50 ⁇ m.
- the preparation of the compositions according to the invention does not present any particular problem, all the usual techniques for preparing these compositions can be used.
- the carbonate and the molybdate can be mixed with the vinylidene fluoride polymer from the polymerization stage, either by direct introduction into the polymerization medium, at the end of polymerization, or even by addition to the wet cake obtained by spin drying or filtration of the aqueous dispersion from polymerization.
- a particularly advantageous procedure consists in adding carbonate and molybdate to the vinylidene fluoride polymer in the form of a powder during the manufacture of a premix, at the same time as the other additives entering into the composition.
- Carbonate and molybdate can also be introduced directly into devices where the vinylidene fluoride polymer is melted, such as screw extruders.
- compositions according to the invention are capable of being used by all the conventional processes for transforming thermoplastic materials. They are particularly suitable for the manufacture of shaped objects intended to be used in fields of application of vinylidene fluoride polymers where a significant reduction in the fumigancy of the shaped objects is particularly advantageous, such as in the building industry and aeronautics (pipes, sheaths, films, paints).
- Example 1 for reference, relates to a composition free of carbonate.
- Examples 2 and 3 relate to compositions according to the invention.
- Example 4 for reference, relates to a composition containing calcium sulphate.
- the formulations evaluated have the following composition, the quantities being expressed by weight: Vinylidene fluoride polymer: 100 Polyethylene wax: 0.2 Calcium molybdate: 0.2 Carbonate (or sulfate): see Table I.
- the vinylidene fluoride polymer is a copolymer of vinylidene fluoride containing 10% by weight of monomeric units derived from a fluorinated olefin of registered trademark SOLEF and of type 11010 produced and marketed by SOLVAY & Cie.
- the calcium molybdate used is in the form of a powder having an average particle size of less than 50 ⁇ m.
- compositions 1 to 4 were prepared by dry mixing of all the ingredients at room temperature in a slow mixer. The mixtures thus obtained were granulated at 190 ° C. From the granules, plates 3 mm thick were pressed which were cut into samples of 0.3 cm x 5 cm x 10 cm. Samples 1 to 4 were then cut into two equal parts, one of which was kept in ambient air (reference sample) and the other of which was immersed for 2 hours in boiling water. After this time, the trichromatic components X, Y, Z of the eight halves of the samples were determined by means of a photometer by measuring the reflectances through amber, green and blue trichromatic filters (illuminant: C, observer 2).
- the HUNTER discoloration difference ⁇ E was then calculated, according to the HUNTER method, between each reference sample and each corresponding sample maintained for 2 hours in boiling water.
- the HUNTER method is exposed in the book by RS Hunter, The Measurement of Appearance, Wiley, 1975.
- the discrepancies in color ⁇ E the values of which are given in Table I in the appendix, make it possible to assess the resistance to storage in a humid atmosphere. 4 compositions evaluated.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
La présente invention concerne des compositions stabilisées au stockage à base de polymères du fluorure de vinylidène comprenant un molybdate de métal.The present invention relates to storage stabilized compositions based on vinylidene fluoride polymers comprising a metal molybdate.
Les polymères du fluorure de vinylidène sont difficilement inflammables et auto-extinguibles. On a déjà proposé d'y incorporer des additifs retardateurs de flamme en vue d'améliorer encore leur résistance à l'inflammation. Néanmoins, les retardateurs de flamme se sont généralement révélés inaptes à empêcher totalement, à température élevée, la combustion des objets façonnés en polymères du fluorure de vinylidène. Par ailleurs, on sait à présent que, contrairement à l'opinion généralement répandue, la combustion des objets façonnés en polymères du fluorure de vinylidène engendre l'émission de fumée en quantité suffisante pour constituer en inconvénient aussi grave que les flammes elles-mêmes, dans la mesure où elle rend plus difficile l'intervention des secours.Vinylidene fluoride polymers are hardly flammable and self-extinguishing. It has already been proposed to incorporate flame retardant additives therein in order to further improve their resistance to ignition. However, flame retardants have generally been shown to be incapable of completely preventing, at high temperatures, the combustion of articles made of vinylidene fluoride polymers. Furthermore, we now know that, contrary to the generally held opinion, the combustion of shaped objects made of vinylidene fluoride polymers causes the emission of smoke in sufficient quantity to constitute as serious a disadvantage as the flames themselves, insofar as it makes rescue operations more difficult.
Dans le brevet FR-A-82 17 123 (SOLVAY & Cie), on décrit l'utilisation de dérivés de molybdène, tels que les molybdates de métaux, pour réduire efficacement la quantité de fumée émise lors de la combustion des polymères du fluorure de vinylidène.In patent FR-A-82 17 123 (SOLVAY & Cie), the use of molybdenum derivatives, such as metal molybdates, is described to effectively reduce the amount of smoke emitted during the combustion of fluoride polymers. vinylidene.
On a maintenant constaté que les compositions à base de polymères du fluorure de vinylidène qui comprennent des molybdates de métaux présentent l'inconvénient de bleuir au stockage en atmosphère humide. Quoique ce bleuissement n'affecte pas l'efficacité fumicide des molybdates de métaux, l'apparition d'une coloration bleuâtre réduit sérieusement les possibilités d'emploi des compositions en cause, notamment dans le domaine du façonnage d'objets incolores ou colorés en teintes claires, tels que les gaines de câbles.It has now been found that the compositions based on vinylidene fluoride polymers which comprise metal molybdates have the drawback of turning blue when stored in a humid atmosphere. Although this bluing does not affect the fumicating efficacy of metal molybdates, the appearance of a bluish coloration seriously reduces the possibilities of using the compositions in question, in particular in the field of shaping of colorless or colored objects in shades clear, such as cable sheaths.
La présente invention, telle qu'elle est caractérisée dans les revendications, a pour but de pallier l'inconvénient précité. A cet effet, elle procure des compositions à base de polymères du fluorure de vinylidène comprenant un molybdate de métal dont le coloris soit stable au stockage en atmosphère humide.The present invention, as characterized in the claims, aims to overcome the aforementioned drawback. To this end, it provides compositions based on vinylidene fluoride polymers comprising a metal molybdate whose color is stable on storage in a humid atmosphere.
Selon l'invention, ces compositions contiennent, comme stabilisant, une quantité efficace de carbonate de métal alcalin ou alcalino-terreux. Tous les carbonates des métaux alcalins ou alcalino-terreux et leurs mélanges conviennent à la réalisation des compositions selon l'invention. On donne néanmoins la préférence aux carbonates des métaux alcalino-terreux tels que, par exemple, les carbonates de calcium, de magnésium ou de baryum. Un carboate de métal alcalino-terreux tout particulièrement préféré est le carbonate de calcium.According to the invention, these compositions contain, as stabilizer, an effective amount of alkali or alkaline earth metal carbonate. All the carbonates of alkali or alkaline-earth metals and their mixtures are suitable for producing the compositions according to the invention. However, preference is given to carbonates of alkaline earth metals such as, for example, calcium, magnesium or barium carbonates. A very particularly preferred alkaline earth metal carboate is calcium carbonate.
La quantité de carbonate présente dans les compositions selon l'invention peut varier dans une assez large mesure. Habituellement, on utilise le carbonate à raison de 1 partie en poids au moins et de 100 parties en poids au plus pour 100 parties de molybdate. De préférence, on l'utilise à raison de 5 à 30 parties en poids au total pour 100 parties de molybdate de métal.The amount of carbonate present in the compositions according to the invention can vary to a fairly large extent. Usually, carbonate is used at a rate of at least 1 part by weight and at most 100 parts by weight per 100 parts of molybdate. Preferably, it is used in an amount of 5 to 30 parts by weight in total per 100 parts of metal molybdate.
Tous les molybdates de métaux et leurs mélanges sont utilisables dans les compositions selon l'invention. A titre d'exemples de pareils molybdates, on peut citer les molybdates de sodium, de bismuth, de calcium, de zinc et d'aluminium. Des molybdates de métaux particulièrement préférés sont les molybdates de calcium, de zinc et d'aluminium.All the metal molybdates and their mixtures can be used in the compositions according to the invention. As examples of such molybdates, mention may be made of sodium, bismuth, calcium, zinc and aluminum molybdates. Particularly preferred metal molybdates are calcium, zinc and aluminum molybdates.
La quantité de molybdate présente dans les compositions selon l'invention peut varier dans une large mesure, notamment en fonction du résultat visé et de la nature du molybdate utilisé. Habituellement, on utilise le molybdate à raison de 0,05 à 2 parties en poids, exprimées en molybdène métallique, pour 100 parties de polymère du fluorure de vinylidène et, de préférence, de 0,10 à 0,50 partie.The amount of molybdate present in the compositions according to the invention can vary to a large extent, in particular depending on the result sought and the nature of the molybdate used. Usually, molybdate is used in an amount of 0.05 to 2 parts by weight, expressed as metallic molybdenum, per 100 parts of vinylidene fluoride polymer and, preferably, from 0.10 to 0.50 part.
Des compositions préférées selon l'invention contiennent donc de 5 à 30 parties en poids de carbonate de métal alcalino-terreux pour 100 parties de molybdate de métal et de 0,10 à 0,50 partie en poids de molybdate de métal, exprimée en molybdène métallique, pour 100 parties de polymère du fluorure de vinylidène.Preferred compositions according to the invention therefore contain from 5 to 30 parts by weight of alkaline earth metal carbonate per 100 parts of metal molybdate and from 0.10 to 0.50 parts by weight of metal molybdate, expressed as molybdenum metallic, per 100 parts of vinylidene fluoride polymer.
Par polymères du fluorure de vinylidène, on entend désigner tous les polymères contenant au moins 85 % molaires, et, de préférence, au moins 90 % molaires d'unités monomériques dérivées du fluorure de vinylidène. Les polymères du fluorure de vinylidène qui conviennent à la réalisation des compositions selon l'invention comprennent donc aussi bien les homopolymères du fluorure de vinylidène que ses copolymères contenant des unités monomériques dérivées d'un ou de plusieurs comonomères. Des résultats particulièrement avantageux sont obtenus avec les polymères du fluorure de vinylidène contenant au moins 90 % molaires d'unités monomériques dérivées du fluorure de vinylidène, le complément éventuel étant constitué de préférence d'unités monomériques dérivées d'autres oléfines fluorées, telles que le fluorure de vinyle, le trifluoréthylène, le chlorotrifluoréthylène, le tétrafluoréthylène et l'hexafluorpropylène.The term “vinylidene fluoride polymers” is intended to denote all the polymers containing at least 85 mol%, and preferably at least 90 mol% of monomer units derived from vinylidene fluoride. The vinylidene fluoride polymers which are suitable for producing the compositions according to the invention therefore include both homopolymers of vinylidene fluoride and its copolymers containing monomeric units derived from one or more comonomers. Particularly advantageous results are obtained with polymers of vinylidene fluoride containing at least 90 mol% of monomeric units derived from vinylidene fluoride, the optional complement preferably consisting of monomeric units derived from other fluorinated olefins, such as vinyl fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene and hexafluorpropylene.
En plus du molybdate et du carbonate, les compositions selon l'invention peuvent contenir tous les additifs usuels des polymères du fluorure de vinylidène, tels que des lubrifiants, des retardateurs de flamme, des additifs polymériques etc. En général, les compositions selon l'invention contiennent au moins 65 % en poids d'un ou de plusieurs polymères du fluorure de vinylidène et, le plus souvent, au moins 80 % en poids de pareils polymères.In addition to molybdate and carbonate, the compositions according to the invention can contain all the usual additives for polymers of vinylidene fluoride, such as lubricants, flame retardants, polymeric additives, etc. In general, the compositions according to the invention contain at least 65% by weight of one or more polymers of vinylidene fluoride and, more often than not, at least 80% by weight of such polymers.
Pour préparer les compositions selon l'invention, le carbonate et le molybdate peuvent être mis en oeuvre sous n'importe quelle forme, en poudre ou en dispersion aqueuse par exemple. Cependant, pour des raisons de commodité, on préfère les mettre en oeuvre sous la forme d'une poudre. Dans ce cas, il est avantageux d'utiliser des poudres ayant une dimension de particules moyenne inférieure à environ 200 µm. De préférence, celle-ci est inférieure à 100 µm et plus particulièrement à 50 µm.To prepare the compositions according to the invention, the carbonate and the molybdate can be used in any form, in powder or in aqueous dispersion for example. However, for reasons of convenience, it is preferred to use them in the form of a powder. In this case, it is advantageous to use powders having a dimension of average particles less than about 200 µm. Preferably, this is less than 100 μm and more particularly than 50 μm.
La préparation des compositions selon l'invention ne présente pas de problème particulier, toutes les techniques habituelles de préparation de ces compositions pouvant être utilisées. Ainsi, on peut mélanger le carbonate et le molybdate avec le polymère de fluorure de vinylidène dès le stade de la polymérisation, soit par introduction directe dans le milieu de polymérisation, en fin de polymérisation, soit encore par addition au gâteau humide obtenu par essorage ou filtration de la dispersion aqueuse venant de polymérisation. Un mode opératoire particulièrement avantageux consiste à ajouter le carbonate et le molybdate au polymère du fluorure de vinylidène sous la forme d'une poudre lors de la fabrication d'un prémélange, en même temps que les autres additifs entrant dans la composition. On peut aussi introduire le carbonate et le molybdate directement dans les appareils où le polymère du fluorure de vinylidène est fondu, tels que les extrudeuses à vis.The preparation of the compositions according to the invention does not present any particular problem, all the usual techniques for preparing these compositions can be used. Thus, the carbonate and the molybdate can be mixed with the vinylidene fluoride polymer from the polymerization stage, either by direct introduction into the polymerization medium, at the end of polymerization, or even by addition to the wet cake obtained by spin drying or filtration of the aqueous dispersion from polymerization. A particularly advantageous procedure consists in adding carbonate and molybdate to the vinylidene fluoride polymer in the form of a powder during the manufacture of a premix, at the same time as the other additives entering into the composition. Carbonate and molybdate can also be introduced directly into devices where the vinylidene fluoride polymer is melted, such as screw extruders.
Les compositions selon l'invention sont aptes à être mises en oeuvre par tous les procédés classiques de transformation des matières thermoplastiques. Elles conviennent tout particulièrement pour la fabrication d'objets façonnés destinés à être utilisés dans des domaines d'application des polymères du fluorure de vinylidène où une réduction notable de la fumigènicité des objets façonnés est spécialement intéressante, tels que dans l'industrie du bâtiment et de l'aéronautique (tuyaux, gaines, filmes, peintures).The compositions according to the invention are capable of being used by all the conventional processes for transforming thermoplastic materials. They are particularly suitable for the manufacture of shaped objects intended to be used in fields of application of vinylidene fluoride polymers where a significant reduction in the fumigancy of the shaped objects is particularly advantageous, such as in the building industry and aeronautics (pipes, sheaths, films, paints).
Les exemples qui suivent illustrent l'invention.The following examples illustrate the invention.
L'exemple 1, de référence, concerne une composition exempte de carbonate. Les exemples 2 et 3 concernent des compositions selon l'invention. L'exemple 4, de référence, concerne une composition contenant du sulfate de calcium.Example 1, for reference, relates to a composition free of carbonate. Examples 2 and 3 relate to compositions according to the invention. Example 4, for reference, relates to a composition containing calcium sulphate.
Les formulations évaluées ont la composition suivante, les quantités étant exprimées en poids :
Polymère du fluorure de vinylidène : 100
Cire de polyéthylène : 0,2
Molybdate de calcium : 0,2
Carbonate (ou sulfate) : voir Tableau I.The formulations evaluated have the following composition, the quantities being expressed by weight:
Vinylidene fluoride polymer: 100
Polyethylene wax: 0.2
Calcium molybdate: 0.2
Carbonate (or sulfate): see Table I.
Dans tous les exemples, le polymère du fluorure de vinylidène est un copolymère du fluorure de vinylidène contenant 10 % en poids d'unités monomériques dérivées d'une oléfine fluorée de marque déposée SOLEF et de type 11010 produit et commercialisé par SOLVAY & Cie.In all the examples, the vinylidene fluoride polymer is a copolymer of vinylidene fluoride containing 10% by weight of monomeric units derived from a fluorinated olefin of registered trademark SOLEF and of type 11010 produced and marketed by SOLVAY & Cie.
Le molybdate de calcium utilisé se présente sous la forme d'une poudre ayant une dimension moyenne des particules inférieure à 50 µm.The calcium molybdate used is in the form of a powder having an average particle size of less than 50 μm.
Les compositions 1 à 4 ont été préparées par mélange à sec de tous les ingrédients à température ambiante dans un mélangeur lent. Les mélanges ainsi obtenus ont été granulés à 190°C. A partir des granules, on a pressé des plaques de 3 mm d'épaisseur que l'on a découpées en échantillons de 0,3 cm x 5 cm x 10 cm. Les échantillons 1 à 4 ont ensuite été découpés en deux parties égales dont l'une a été conservée à l'air ambiant (échantillon de référence) et dont l'autre a été plongée pendant 2 heures dans l'eau bouillante. Après ce laps de temps, on a déterminé, au moyen d'un photomètre, les composantes trichromatiques X, Y, Z des huit moitiés d'échantillons par mesure des réflectances au travers de filtres trichromatiques ambre, vert et bleu (illuminant : C, observateur 2°). A partir des composantes trichromatiques, on a ensuite calculé, suivant la méthode de HUNTER, l'écart de coloration ΔE entre chaque échantillon de référence et chaque échantillon correspondant maintenu pendant 2 heures dans l'eau bouillante. La méthode de HUNTER est exposée dans l'ouvrage de R.S. Hunter, The Measurement of Appearance, Wiley, 1975. Les écarts de coloration ΔE dont les valeurs sont reprises au Tableau I en annexe permettent d'apprécier la résistance au stockage en atmosphère humide des 4 compositions évaluées.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT87202405T ATE61808T1 (en) | 1986-12-15 | 1987-12-03 | STORAGE STABILIZED COMPOSITIONS BASED ON METAL MOLYBDATE CONTAINING VINYLIDE FLUORIDE POLYMERS. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8617622 | 1986-12-15 | ||
| FR8617622A FR2608165B1 (en) | 1986-12-15 | 1986-12-15 | STORABLE STORAGE COMPOSITIONS BASED ON VINYLIDENE FLUORIDE POLYMERS COMPRISING A METAL MOLYBDATE |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0275579A1 true EP0275579A1 (en) | 1988-07-27 |
| EP0275579B1 EP0275579B1 (en) | 1991-03-20 |
Family
ID=9341971
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP87202405A Expired - Lifetime EP0275579B1 (en) | 1986-12-15 | 1987-12-03 | Storage-stabilized compositions based on vinylidene fluoride polymers containing a metal molybdate |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4786662A (en) |
| EP (1) | EP0275579B1 (en) |
| JP (1) | JP2509959B2 (en) |
| AT (1) | ATE61808T1 (en) |
| DE (1) | DE3768798D1 (en) |
| ES (1) | ES2021351B3 (en) |
| FR (1) | FR2608165B1 (en) |
| GR (1) | GR3001633T3 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998059387A2 (en) * | 1997-06-23 | 1998-12-30 | Solvay (Societe Anonyme) | Lithium batteries |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2534264B1 (en) * | 1982-10-11 | 1985-10-31 | Solvay | COMPOSITIONS BASED ON VINYLIDENE FLUORIDE POLYMERS HAVING REDUCED FUMIGENICITY |
| DE3738060A1 (en) * | 1987-11-09 | 1989-05-18 | Henkel Kgaa | STORAGE STABLE ADHESIVE FOR ESPECIALLY RECHLORINATED PVC PLASTICS |
| US5749614A (en) * | 1995-12-04 | 1998-05-12 | Motorola, Inc. | Vacuum pickup tool for placing balls in a customized pattern |
| US20030035138A1 (en) * | 2001-08-17 | 2003-02-20 | Schilling Mary K. | Internet-based custom package-printing process |
| US20090263671A1 (en) * | 2008-04-21 | 2009-10-22 | Kui Yao | Ferroelectric Poly (Vinylidene Fluoride) Film on a Substrate and Method for its Formation |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0107220A1 (en) * | 1982-10-11 | 1984-05-02 | SOLVAY & Cie (Société Anonyme) | Polyvinylidene fluoride compositions with reduced fume production |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL46931C (en) * | 1936-09-11 | |||
| BE459043A (en) * | 1940-09-27 | |||
| NL143973B (en) * | 1965-03-08 | 1974-11-15 | Raychem Corp | PROCESS FOR MAKING POLYURETHANES AND OBJECT FROM A POLYURETHAN MADE THEREFORE FLAME-PROOF. |
| JPS5699232A (en) * | 1980-01-11 | 1981-08-10 | Kureha Chem Ind Co Ltd | Preparation of halogen-containing resin particle of high apparent density |
| JPS5837040A (en) * | 1981-08-28 | 1983-03-04 | Ishikawajima Harima Heavy Ind Co Ltd | Fire-retardant resin in concentrated oxygen |
| US4532289A (en) * | 1983-11-28 | 1985-07-30 | Sermatech International, Inc. | Primer coating composition |
-
1986
- 1986-12-15 FR FR8617622A patent/FR2608165B1/en not_active Expired
-
1987
- 1987-12-03 AT AT87202405T patent/ATE61808T1/en not_active IP Right Cessation
- 1987-12-03 ES ES87202405T patent/ES2021351B3/en not_active Expired - Lifetime
- 1987-12-03 DE DE8787202405T patent/DE3768798D1/en not_active Expired - Lifetime
- 1987-12-03 EP EP87202405A patent/EP0275579B1/en not_active Expired - Lifetime
- 1987-12-03 US US07/128,106 patent/US4786662A/en not_active Expired - Lifetime
- 1987-12-15 JP JP62317304A patent/JP2509959B2/en not_active Expired - Lifetime
-
1991
- 1991-03-21 GR GR90401149T patent/GR3001633T3/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0107220A1 (en) * | 1982-10-11 | 1984-05-02 | SOLVAY & Cie (Société Anonyme) | Polyvinylidene fluoride compositions with reduced fume production |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998059387A2 (en) * | 1997-06-23 | 1998-12-30 | Solvay (Societe Anonyme) | Lithium batteries |
| WO1998059387A3 (en) * | 1997-06-23 | 1999-03-18 | Solvay | Lithium batteries |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3768798D1 (en) | 1991-04-25 |
| GR3001633T3 (en) | 1992-11-23 |
| ES2021351B3 (en) | 1991-11-01 |
| FR2608165B1 (en) | 1989-03-03 |
| FR2608165A1 (en) | 1988-06-17 |
| JPS63156846A (en) | 1988-06-29 |
| EP0275579B1 (en) | 1991-03-20 |
| US4786662A (en) | 1988-11-22 |
| ATE61808T1 (en) | 1991-04-15 |
| JP2509959B2 (en) | 1996-06-26 |
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